JPS6136238A - Manufacture of unsaturated compounds alpha_substituted in beta_position of two electron_withdrawing groups - Google Patents

Abstract

Compounds of formula <IMAGE> (Ia) or <IMAGE> (Ib) in which n denotes an integer from 1 to 10 and X and Y, which are identical or different, each denote an electron-attracting group, are made by reacting a halogenating agent with a compound of formula <IMAGE> (IIa) or <IMAGE> (IIb) in which R, X and Y are as hereinbefore defined, anionized by a base.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the formula: [wherein n represents an integer of 1 to 10, and X and Y are the same or different, and each of ,-CONl
'h R4, -CN.

represents an electron-withdrawing group selected from -3O2R5 and -NO2, where R+, R2, R3, R4 and R5 each represent an alkyl group having 1 to 4 carbon atoms, and R5 is unsubstituted. or a thunyl group substituted by methyl] is provided.

Of particular interest are compounds of general formula Ia and more in which one of the symbols X and Y represents 10ORI and the other represents -GOOR2.

European Patent Application EPOO 82781 discloses that the corresponding β- 1 shows a method for producing α-chloro-β-ketoesters by reaction with a ketoester.

P, L, Stotter and A,
Hill's Tetra T-Doron Letters
Trahed Letters), No. 40
．． 4087 (1972), α-chloro-β-
It is known to prepare ketoesters from the corresponding β-ketoesters by reaction with sodium hydride and subsequent rapid reaction with bromine in methylene chloride at 0°C.

However, in particular M. L. Poutsma, The Journal of the American Chemical Society (J.

Amer, Chem, Soc,), Dan1to (19
), 4285 (1965), it is known that when ethylene compounds are chlorinated with chlorine in the presence of oxygen at room temperature, substantially allyl-substituted products are also formed in addition to the products.

According to U.S. Patent No. 2,995,600, myrcene is chlorinated with gaseous chlorine to produce 3-chloro-2-methyl-6-
Methylene-1,7-ofcudiene is produced.

From U.S. Pat. No. 4,272,412, it is shown that chlorination of dihydro-α-ionone with in situ prepared hypohalous acid produces 4-(5 It is also known that -chloro-6-methylene-2,2-dimethylcyclohexyl)-2-butanone is produced.

Additionally, a halogenating agent such as molecular chlorine or sulfuryl chloride can be added to a compound of formula (II a
) or (n b), where n, X and Y are as defined above, no formation of α-chlorinated compounds with respect to the X and Y groups is observed. Only halogenated products of the terpene chains are produced.

Compounds of formula (IIa) or (IIb) are anionized with a base and a halogenating agent capable of supplying a CI'' cation, wherein n, X and Y are as defined above I have now discovered that it can be obtained by reacting with
And this is the subject of the present invention.

In the process of the invention, it is particularly advantageous to add the anionizing agent and the halogenating agent to the compound of formula (TI a) or (n b) in solution in a suitable anhydrous organic solvent.

It is also possible to first anionize the compound of formula (IIa) or (Ilb) and then add the halogenating agent.

Particularly suitable anionizing agents include alkali or alkaline earth metals (eg sodium).

(potassium or calcium) hydrides, amides,
hydroxides and carbonates, as well as non-quaternized amines (e.g. 1,8-diazabicyclo[5,4,0
] undec-7-ene (DBU), collidines, ethyldiisopropylamine or ethyldicyclohexylamine).

Organic solvents include aliphatic hydrocarbons (e.g. pentane or hexane), aromatic hydrocarbons (e.g. benzene or toluene), ethers (e.g. ethyl ether, methyl tert-butyl ether or tetrahydrofuran), ketones (e.g. acetone or methyl isobutyl ketone). , a tertiary amide (e.g. dimethylformamide or N-methylpyrrolidone), a nitrile (e.g. acetonitrile), a diluted solvent (e.g. nitrobenzene or nitromethane), or the reaction can be carried out using e.g. tetrabutylammonium hydrogen sulfate. When carried out in the presence of a phase transfer catalyst such as a polychlorinated solvent (eg methylene chloride).

The halogenating agent is the source of 01+ cations and is preferably molecular chlorine, sulfuryl chloride, N-chlorosuccinimide or hexachloroethane.

The process is generally carried out at temperatures between 0 and 120°C, and preferably 2
It is carried out at a temperature of around 5°C.

The process according to the invention can also be carried out using an alkali metal alcoholate (eg sodium methylate) as anionizing agent in the corresponding alcohol (eg methanol). However, under these conditions anionization and halogenation preferably occur below 0°C, generally below -30°C, and especially below -50°C.
It should be carried out at a temperature in the vicinity.

Stoichiometric amounts of anionizing and halogenating agents are generally used with respect to the compound of formula (Tla) or (nb) used.

Formula (Ia) or (Ib) obtained by the method of the invention
The products can be isolated from the reaction medium by conventional extraction methods and purified by the application of physico-chemical methods such as distillation or chromatography.

Compounds of formula (IIa) or (IIb) (7) are prepared under the conditions described in European Patent 0044771 with an active methylene group of the formula where X and Y are as defined above. It is obtained by selective addition of butadiene of the formula where n is as defined above to the containing compound.

Compounds of formula (Ia) or (Ib) are of particular interest as intermediates in organic chemistry.

For example, compounds of formula (Ia) or (Ib) in which one of X and Y represents -COCH3 and the other represents -GOOR2 are ethylene compounds of the formula where n is as defined above. Ketones can be used to produce ketones in the form of mixtures of EE and EZ isomers.

In the compounds of formula (V), one of symbols X and Y is -CO
The formula (I
Decarboxylation of a compound of a) or (Ib) to produce an α-haloketone of formula, where n is as defined above, which is then dehalogenated to produce a compound of formula (V) can be produced in particular by producing a product of

Decarboxylation and dehalogenation are carried out using the general formula (IV
It is also possible to carry out without isolating the α-haloketone of a) or (IVb).

Sequential or simultaneous decarboxylation and dehalogenation reactions can be carried out under the conditions described in European patent application EP 82781. For example, a compound of general formula (V) where n=1 is a pseudoionone, which can be converted to vitamin A using known methods.

The following examples illustrate the invention.

Example 1 (CH3)2 C=CH-CH2CH2-C(=CH2
) -CH2-CH2-CI (C00CH3)OCH
3 and (CH3)2G-〇H-CH2CH2-C(CH3)=
A mixture of CH-CHz-OH(COOCH3)COH3 (2.52 g; 0.01 mol) was added into a 100 cc round bottom flask under an argon atmosphere and then ground potassium hydroxide (0.6 g; 0107 moles)
and hexachloroethane (2.5 g; 0.0105 mol) were added. The mixture was stirred at 25°C for 12 hours. The reaction mixture was poured into water (100cc) and then extracted with ethyl ether (3X30cc). The organic phases were combined and dried over magnesium sulphate. After filtration and evaporation of the solvent a pale yellow oil (3.75 g) was obtained.

Under reduced pressure (0, lmmHg; 0.

013 kPa) at 150°C, (CH
3) 2C=CH-CH2CH2-C(<H2)CH2
CH2-CG I (COOCH3)oco3 and (OH3)2 C=CH-CH2CH2-CCCH3)
=CH-CH2-CTCI (000CH:+)0G
A 55/45 mixture (2.5 g) of H3 was produced, which was 81
%.

The yield of isolated products was 70%.

Example 2 N-methylpyrrolidone (50c c) and Q (C; H3)2 C=CH-CH2CH2-C(=CH
2) -CH2-CH2-CH(CODCH3)COC
H3 and (CH3)2c=cH-CH20H2-C(CH3)=
A 55/45 mixture of CH-CH2-OH(COOGIh)0CII3 (5,5 g; 0,0218 mol) was added into a 100 cc round bottom flask under an argon atmosphere, and then sodium carbonate (2,49 g; .02
35 mol) and hexachloroethane (5.24 g; 0
．． 0221 mol) was added. The mixture was stirred at 25°C for 20 hours.

A white precipitate was seen to form. After filtration, the reaction mixture was poured into water (150cc) and then extracted with ethyl ether (3X50cc). The organic phases were combined and dried over sodium sulfate. After filtration and evaporation of the solvent, (CH3)2 C=CH-CH2CH2-G(=CH2
)-C12-CH2-C(II (COOCH3)CO
CH3 and CCH3)2 G = CH-CH2CH2-C(CH3
) <OCH2-GOI (C00GH3) A pale yellow oil (7°47g) consisting of a 55/45 mixture of OCH3
was gotten.

Analysis by gas phase chromatography using an internal standard is The conversion rate is 98%, The yield rate is 97% showed that.

Tsutomu A N-Methylpyrrolidone (50cc) and (CH3)
2 C=CH-CH2Glh -C(=CH2) -C
H20H2-CH(C[1OCH3)GoCT.

and (Ill; H3)2 C=CH-CIH2CH2-G
(CH3)<H-CH2-OR(COOCH3)OCH
A 55/45 mixture of 3 (4.8 g; 0.0190 mol) was added into a 100 cc round bottom flask under an argon atmosphere and then ground potassium hydroxide (1.10 g; 0.0190 mol)
01964 mol) and hexachloroethane (5 g; 0
．． 021 mol) was processed. The mixture was stirred at 25°C for 40 minutes. The reaction mixture was poured into wood (100 cc) and then extracted with ethyl ether (3X50 cc). The organic phases were combined and dried over sodium sulfate. After filtration and evaporation of the solvent, a slightly yellow oil (8°2 g) was obtained, which was (CH3)2 C=CH-CH2CH2-G (=CH
2) CH2-CH2-CC1(COOGIh)OCH
3 and (CH3)2 C=CH-CIH2CH2-C(C11
3)=CH-CH2-Cc1 (COOCH3)0G
It contained a 55/45 mixture of H3.

Analysis by gas phase chromatography using an internal standard showed that the conversion was in the range of 98-99%, with a yield of -90%.
%.

Joseso A Hexane (15cc), N-methylpyrrolidone (5cc
), potassium hydroxide (0.56 g; 0°01 mol),
And then (CH3) 2 C<H-CI20H2-G (=CH
2) CH2-CH2-OH(COOCIh)0GH3 and (C)13)2c=cH-CH2CH2-C(CH3)
=CH-CH2-0H(COOCH3)coco:+ 55/45 mixture (2,52 g, 0.01 mol),
Added to a 100cc round bottom flask under an argon atmosphere. Hexachloroethane (2°36g; 0.01 mol)
was added next. The mixture was stirred at 25°C for 15 hours. The reaction mixture was poured into water (100cc) and then extracted with ethyl ether (3X50cc). - The combined organic phases were dried over magnesium sulphate. After filtration and evaporation of the solvent (CH3)2C=CH-CH2CH2-G (=C
H2)-CHz[l:To-CC1(C[1OCH+
) COC, I3 and (CH3)2 C=CH-OH2CH2-G (CH3
)=GH-CH2-C[I (COOCH3)OCH3 pale yellow oil (3°97g) consisting of a 55/45 mixture of
was gotten.

The yield of isolated product after flash distillation was 70%.

Example 5 N-methylpyrrolidone (20cc) and (CD3
)2 C=CH-Glh CH2-C(<I2) 00
20 month 2-CI(COOCH3)OCH3 and (OH3)2G=GH-OH2CH2-C(CH3)<
)I-CTo-CI(COOCTo)OCH3 (2,52 g; 0.01 mol),
under an argon atmosphere into a 100 cc round bottom flask and then potassium carbonate (1.5 g; 0.0108 mol) and hexachloroethane (2.36 g; 0.01
mol) was added. The mixture was stirred at 25°C for 24 hours.

The reaction mixture was poured into a loocc and then extracted with ethyl ether (3X50cc). - The combined organic phases were dried over magnesium sulphate. After filtration and evaporation of the solvent (CH3)2 C=CH-OH2GH? -C(=CH2
) -C:Hz Glh (:G 1 (C:0OCH
s ) OCH3 and (CH3)2 C=CH-CI2 OH2-G (CH
3)=CH-CH2-CCI (COOCH3)0CI
A pale yellow oil (3 g) was obtained consisting of a 55/45 mixture of h.

The conversion rate was 80%.

The yield of isolated product was 73%.

Example 6 Tetrahydrofuran (20cc) and (CH3)2
C=CH-OH2GH? -G (=CH2)CH2
OH2-CI (C[1OCH3)CDCI:+ and (CH3hG=GH-C:1hcH2-C(G)+3)
=C)l-C)+2-C)l(GO(ICl3)0CH
3 (7) 55/45 mixture (2,52 g; 0.01 mol)
was added to a 100 cc round bottom flask under an argon atmosphere and then potassium hydroxide (0.56 g; 0.0
1 mol) and hexachloroethane (2.5 g; 0.0
105 mol) was added. The mixture was stirred at 25°C for 10 hours. The reaction mixture was poured into water (100cc) and then extracted with ethyl ether (3X50cc). - The combined organic phases were dried over sodium sulfate. After filtration and evaporation of the solvent (CH3)2C=CH-Cl2CI2-C(=CI
2)-OH2GH2-GCI (COOCH3)OCH
3 and (CH3)2 C=CH-CH2CH2-C(CH3)
A slightly yellow oil consisting of a 55/45 mixture of =CHCOOCH2CCI (COOCH3)0CHx was obtained.

The yield of isolated product was 70%.

Example 7 Methanol (20 cc) and small portions of sodium (0.23 g; 0.01 gram atom) were added into a 100 cc round bottom flask under an argon atmosphere. The mixture was cooled to -50°C and then (OH3)2C=CH-Cl2CH2-C(=(lJ
Iz)OH2G)I? -CH(0000)! s)0
CIh and (CH3)2 C=CH-OH2OH2-C(CH3)
A 55/45 mixture of =CH-CH2-OH(COOCH3)OCH3 (2.52 g, 0.01 mol) and N-chlorosuccinimide (1.33 g; 0.01 mol) were added. The mixture was stirred at -50°C for 40 minutes. After evaporation of methanol, the reaction mixture was poured into water (100 cc) and then extracted with ethyl ether (3×50 cc). - The combined organic phases were dried over magnesium sulphate. After filtration and evaporation of the solvent and after flash distillation, (CH3)2C=CH-CH2CH2-C(=CH2
)GHz CH2-GOl (GOOGHa) COC
:Ih and (CH3)2 C=CH-CH2CH2-C(CH3)
A pale yellow oil (2.5 g) consisting of a 55/45 mixture of =CH-CH2-CC1(COOCH3)OCH3 was obtained.

The yield was 87%.

Example 8 Hexane (500cc) and sodium amide (4
,04g; 0.103 mol) under an argon atmosphere,
1. It was added into a 200 cc reactor. The mixture was cooled to 5°C and then (CH3)2C=CH-C)rh
CTo -C(=CH2)C)12 CI(2-(H(
C00CH3)0C113 and (CH3)2 C=CH-CH2CH2-C(CH3)
-CH-CH2-CH(COOCH3)COCT.

A warm solution of a 55/45 mixture (24.4 g; 0.097 mol) in hexane (100 cc) was added slowly over 1 hour and 40 minutes. The mixture was then allowed to stir for 5 hours at 5°C, resulting in the evolution of 95% of the theoretical amount of ammonia. A warm solution of sulfuryl chloride (14.5 g; 0.107 mol) in hexane (50 cc) was then added over 45 minutes. The mixture was stirred for 1 hour and 30 minutes and a white precipitate was seen forming. After filtration and evaporation of the solvent, (CH3)2 C-CH-CH2CH2-C(=CH2
)CH2CH2-GOl (GOOGHa)OCH3 and (C:H3)2 C=CH-CH2CH2-C(CH3
) = GH-GH2-CCl (COOCH3)0GH3 pale yellow oil (31°2 g) consisting of a 55/45 mixture of
was gotten.

Measurement by gas phase chromatography using an internal standard is One conversion rate is 93.5% The yield rate is 90.2% showed that.

Example 9 Toluene (a o c c) and sodium amide (
0.76 g; 0.0194 mol) was added into a 250 cc reactor under an argon atmosphere. Mixture 5-10
'0 and then (CH3)2 C=CH-CH2CH2-C(=CH2
)CH2C)12-OH(GOOGHa)OCH3 and (CH3)2C=CH-CH2CH2-C(CH3)=
55/45 mixture of GH-GH2-CH(GOOGHa)0CHt (4,96 g; 010197 mol)
of toluene (20 cc) was added. 2 of the mixture
React for 2 hours at 5°C and then add sulfuryl chloride (2
, 89g; 0°0215 mol) of toluene (lOCC)
Added medium temperature liquid. The mixture was stirred for 1 hour. After filtration and evaporation of the solvent, (CH3)2 C=CH(:H2CH2-CC=CH2
)CH2CH2-CC1(COOCH3)COCT.

and (CH3)2 C=CH-CH2CH2-C(CH3)
= CI-CH2-CG I (COOCH3)OCH3 A pale yellow oil (5°63g) consisting of a 55/45 mixture of OCH3
was gotten.

Analysis by gas phase chromatography using an internal standard is
It showed that the yield was 66.8%.

Example U Methanol (20cc) and portions of sodium (0.23g; 0.01 gram atom) were added into a 100cc round bottom flask under an argon atmosphere. The mixture was cooled to -50'0 and then (CH3)zC=CH-C:I2CH2(:(=CI2
)CH2CH2-OH(COOCH3)COC:H+ and (CH3)2G=GH-CH2CH2-C(CH3)=
A 55/45 mixture of CH-CH2-OH(COOCH3)OCH3 (2,52 g; 0.01 mol) was added.

Next, add sulfuryl chloride (1.34 g; 0.01 mol) to -
It was added at a temperature of 50°C. The mixture was stirred at -50°C for 30 minutes. After raising the temperature naturally to about 20°C,
The reaction mixture was poured into water (100cc) and then extracted with ethyl ether (3X50cc). - The combined organic phases were dried over magnesium sulfate. After filtration and evaporation of the solvent, (CH3) 2 C=CH-CI2 CI2-G (=
CH2)-CH2CH2-CG I (COOCH3)
0Glb and (CH3)2 C=CH-CI20H? -C(CH3)
Yellow oil (4,7 g) containing a 55/45 mixture of <H-CH2-CG l (COOCH3)0GH3
)was gotten.

The yield of isolated product was 65%.

Example 11 Methanol (20cc) and sodium (0.23g
;0.01 gram atom) under an argon atmosphere,
Added into a 0cc round bottom flask. The mixture was cooled to OoC and then (CH3)2C=CH-CI2C
I2-C(=CH2) -CTo CI2-CI (C
OOCH3)0GHz and (GHzhC=GH-CH2O)12-C:(CH:+
)=CH-C)[2-CI(COOCH3)0GH3 (2,52 g; o, 01 mol) and N-chlorosuccinimide (1.33 g; 0.01 mol) were added. The mixture was stirred at 0°C for 40 minutes. After evaporation of methanol, the warm mixture was poured into water (100 cc) and then extracted with ethyl ether (3×50 cc).

=-The combined organic phases were dried over magnesium sulphate.

After filtration and evaporation of the solvent a yellow oil (2°3 g) was obtained which, according to analysis by gas phase chromatography, contained -6.5% of starting material, -41.6% of (CH3)2 C=CH- CI2 CH2-C(=CI
2)-GH? CH2-CHCl-COOCH3 and CCH3)2C=CH-CI20H2-C(ell:
+)=CH(:I2-CHG 1-COOCH3-5
5/45 mixture, -51,8% of (CH3)2C=CH-CI2CH2-G (=
CH2)-CI2 CI2-CO] (GOOCH3)
0cH3 and (CH3)2 C=CH-CI2 CI2-C(CH3
)=GH-Glh-CGI (COOCHa)OC
It contained a 55/45 mixture of H3.

Example: Sodium hydride (:o,!5g; 0.01 mol) was added to 100 cc in mineral oil at a concentration of 50% under an argon atmosphere.
Added into a round bottom flask. Dry it with pentane (3X2
0cc). Tetrahydrofuran (20cc
) and (CH3) 2 C=CH-CH2CH2-C(=CH
2)-CI(2CH2-GH(COOCH3)C(lc
H3 and (CH3)2 C=CH-CH2CH2-C(CH3)
A 55/45 mixture of <H-CH2-OH(GOOfll:I3)OCH3 (2,52 g, 0.01 mol) was then added. The mixture was allowed to react at 25° C. for 5 hours, and then a warm solution of sulfuryl chloride (1.34 g; 0.01 mol) in tetrahydrofuran (10 cc) was slowly added.

The mixture was stirred at 25°C for 3 hours. The reaction mixture was diluted with water (1
00CC) and then ethyl ether (3X
50cc). - The combined organic phases were dried over magnesium sulphate. After filtration and evaporation of the solvent a yellow oil (3.0 g) was obtained which, according to analysis by gas phase chromatography, contained 62% of (CH3)2C=CH-CH2CH2-C(=CH2
)CH2OH2-GCI (COOCH3)OCH3 and (CTo)2C<H-CIh CH2-C(CH3
)=CH-CH2-CC1(CODCH3)OCH3.

According to analysis by gas phase chromatography, the yield is 75
%Met.

Example 13 Dry ether (40cc), sodium (0°236g
;0.01029 gram atom) and 2.3 ferric chloride crystals were added into a 100 cc round bottom flask under an argon atmosphere.

(CH3) 2C=CH-CI20H2-C(<I2
) CI2 GTo -CI (C00GH3)CO
C.T.

and (OH3)zG=cH-OH2GHz-C(OH3)=
A 55/45 mixture of CH-OH2-CI(COOCH3)0GH3 (2.42 g, 0.00961 mol) was then added. The mixture was reacted for 4 hours at 25°C.

After cooling to 0°C, sulfuryl chloride (1,30g;
．． A solution of 0.00963 mol) in ether (5cc) was added. The mixture was stirred at 0°C for 30 minutes. The reaction mixture was poured into water (100cc) and then extracted with ethyl ether (3X50cc). - The combined organic phases were dried over magnesium sulphate. After filtration and evaporation of the solvent, (CH3)2C=CH-CToOH2-C(=CH
2) CH2OH2-Cel (CODCH3)OCH3 and (OH3)2C=CH-CH2CH2-C(CH3
) =CH-CH2-CC1(CODCH:+)OC
Yellow oil (2°71 g) consisting of a 55/45 mixture of H3
was gotten.

Analysis by gas phase chromatography using an internal standard is One conversion rate is 74.8% -The yield is 67% showed that.

Example 14 Dimethylformamide (,200cc), potassium carbonate (16.4g; 0.118 mol), (OH3)2C=
CH-OH2CH2-G (=CI2)-CH2CH
2-CH(COOCH3)OCH3 and (OH3)2 C=CH-CH2CH2-C(CH3)
A 55/45 mixture of =CH-CH2-C:H(CODCH3)0GH3 (25.2 g, 0.1 mol) and N-chlorosuccinimide (14 g; 0° 104 mol) were added in 500 cc under an argon atmosphere. Added into a round bottom flask. The mixture was reacted at 25°C for 16 hours. The reaction mixture was poured into water (100cc) and then extracted with ethyl ether (3X50cc). - The combined organic phases were dried over magnesium sulphate. A slightly yellow oil (27 g) was obtained after filtration and evaporation of the solvent, which contained 75% of (Cab)2G(:1t-OH2GH2-C(=C
H2) -OH2CH2-GCl (C00CTo)
OCH3 and (CH3)2 C=CH-CH2(JI2-CCCH3
)=CH-OH2-001(COOCH3)OCH3.

Implementation - Twisting↓j Dimethylformamide (150cc), potassium carbonate (
27.6 g; 0.2 mol), and (CH3) 2 C
<H-CH2CH2-C(<I2) -OH2OH2
-CH(CODCH3)0GH3 and (CH3h C=CH-CH2C1b -C(C)I3
)=CH-CH2-cH(GOOCR3)COOH3 A 55/45 mixture (38 g; 0.15%) was added into a 500 cc round bottom flask under an argon atmosphere, and then hexachloroethane (42 g; 17
7 mol) was added. The mixture was stirred at 25°C for 15 hours. Water (200 cc) was added and the mixture was then extracted with ethyl ether (3x50 cc). - The combined organic phases were dried over magnesium sulphate. After filtration and evaporation of the solvent an oil (60 g) was obtained which was purified under reduced pressure (1
mmHg; 0.13 kPa), 94% of CCH3)2 C=CH-CH201b -CC=CH
2) CTo CH2-GC] (COOCH3)OCH
3 and (CH3)2 C-CH-CI2 CH2-C(CH3
)=CH-CH2-CG I (COOCH3)OCH
An oil containing a 55/45 mixture of 3 was produced.

The yield of isolated product was 81%.

The structure of the obtained product was determined by proton nuclear magnetic resonance spectroscopy).
Confirmed by

Xmu square 1j Methyl tertiary butyl ether (20cc), potassium carbonate (1.5g; 0゜0108
mole), and (CTo)2C=CH-CH2CH2-CCHCH
2) CI2CH7-OH(GOOCR3)GOCT.

and (CH3)2C=GH-CH2CH2-C(CH3)=
A 55/45 mixture (2,52 g; 0.01 mol) of CH-CH2(:H(GOOCR:+)COCH+
under an argon atmosphere into a 200'cc round bottom flask and then N-chlorosuccinimide (1,33
g; 0.01 mol) was added. The mixture was reacted at 25°C for 15 hours. Water (100cc) was added and the mixture was extracted with ethyl ether (3X50cc). - The combined organic phases were dried over magnesium sulfate. A colorless oil (2,3 g) was obtained after filtration and evaporation of the solvent, which contained 91% of (CH3)2C=CH-CH2CH2-G(=CH2
) CH2CH2-cC1(C:00GH:+)OC
H3 and CCH3)2 C=CH-CH2CH2-C(CH5)
It contained a 55/45 mixture of =CH-CH2-GOL (GOOCR3)0GH3.

The yield of isolated product was 73%.

Example 17 N-methylpyrrolidone (20cc), potassium carbonate (2
, 8 g, 0.0202 mol), and CH2=C(CH
3) -CI2CH2-CH(COOCH3)COt
ll:H:+ and (CH3)2C=GH-CH2(:■(GOOCR3)
COCT.

A 55/45 mixture of (3,68 g; 0.02 mol) was added into a 100 cc round bottom flask under an argon atmosphere, and then hexachloroethane (5 g, 0.02 mol) was added to a 100 cc round bottom flask under an argon atmosphere.
0211 mol) was added. The mixture was reacted at 25°C for 15 hours. Water (100 cc) was added and the mixture was extracted with ethyl ether (3x50 cc). - The combined organic phases were dried over magnesium sulfate. After filtration and evaporation of the solvent a pale yellow oil (6.4 g) was obtained,
It contains 16% starting material as well as 41% CH2=C(CH3)-CH2CH2-CGI CH2
CH2) COCT.

and (CH3) 2 C=CH-CH2-CG I CH2
CH2) contained a 55/45 mixture of COCIh.

The yield was 83% based on reacted starting material.

N! 8 Acetone (80cc), potassium carbonate (8゜28g; 0
．． 05993 mol), hexachloroethane (1'3.1
7g; 0.05565 mol), 42゛ and (CH3)2G-4;H-CH2CH2-G (=C
To) -CI2 CH2-CH(GOOCH3)C
OC:T.

and (CHt)2C-CH-CH2CH2-C(CH3)=
A 55/45 mixture of CH-CH2-OH(COOCH3)OCH3 (10.86 g, 0.04312 mol) was added into a 250 cc round bottom flask under an argon atmosphere and then at the reflux temperature of the reaction mixture. Stirred for 7 hours. Water (100cc) that made the reaction mixture slightly acidic
and then ethyl ether (3X50cc
) was extracted. −The combined organic phase is magnesium sulfate−
Dry with L. After evaporation of the solvent, an orange-yellow liquid (15,
45 g) was obtained, which is (CH3)2 C=CH-CH2CH2-C(=CH2
)-CH2CH2-C:CI (COOCH3)0CI
h and (CM: + h C=CH-CH2CH2-C(CH3
) =CH-CH2-COI (COOCH3)OCH
It contained a mixture of 3.

The yield was 91.5% according to analysis by gas phase chromatography using an internal standard.

Nidimethylformamide (20 cc), hexachloroethane (2.5 g; 0.0105 mol), and (CH3)2 C=CH-CH2CH2-C(=CH2
) CTo CH2CH(COOCH3) COCH3 and (CH3)2CtomiCH-CI2 CH2-C(C:I3
)=CH-CH2-OH(COOCH3)COH3 (2,52 g; 0.01 mol),
under an argon atmosphere into a 10cc round bottom flask and then 1,8-diazabicyclo-[5,4,0]
Undec-7-ene (DBU) (2 g; 0.0131 mol) was added. The mixture was stirred at 25°C for 4 hours. The reaction mixture was poured into water (100cc) and then extracted with ethyl ether (3X50cc). - The combined organic phases were dried over magnesium sulphate. After filtration and evaporation of the solvent, a pale yellow oil (4°12 g) was obtained which, after flash distillation, contained 87% of (C:I3)2C=CH-CI2CH2-C(
=CH2)CI2 CH2-0C1(COOCH3)0
CHa and (CH3)2 C=CH-CI20H2-C(CH3)
=GH-GH2-CCI (GOOCH3)CH2CH
A pale yellow oil containing a 55/45 mixture of 2 (2, 4
1g).

The yield of Qi separated product was 73%.

Example 20 Hexachloroethane (7.11 g; 0.03 mol), tetrabutylammonium hydrogen sulfate (0°342 g; 0.03 mol).
001 mol), as well as (CO:+hC=CH-CH7-CC<To)- dissolved in methidine chloride (50cc)
C:Ih CH2-C:H(COCH3)000G)j
3 and (C1b)2C=C1(-CH2-C(CH3)
<H-CH2-CIl (COCH3) A 55/45 mixture of COOCH3 (2,52 g; 0.01 mol) was added into a 100 cc round bottom flask under an argon atmosphere. An aqueous solution (5cc) containing 50% by weight of sodium hydroxide was then added and the mixture was stirred vigorously for 2 hours at 25°C.

After extraction and chromatography of the reaction mixture, (CT
o) 2C=CH-CH2-C(=CH2)-CI2CH
2-CC1(COCH3)-GOOCH:+ and (CH3)2C=CH-CH2-G(CHs)=
A 55/45 mixture (1,62 g) of CH-CH2-GCI (COCH3) -0OCH3 was obtained.

The yield was 56.5%.

Example 21 Hexachloroethane (3.08 g), potassium carbonate (2
, 07g) and tetrabutylammonium sulfur butyhydrogen (
0.34 g) was added into a 100 cc round bottom flask under an argon atmosphere. Next (CH3)2 C=CH-C
To -C(=CH2)-CC0CH5-CH(GOC
H3)0OGH3 and (CH3)7 C=CH-CH2-C: (C)13
) =CH-CH2-CH(COCH3)0000)+
A 55/45 mixture of 3 (2.52 g; 10 mmol) was added. The reaction mixture was heated under reflux for 5 hours.

(CH:+hC:=CH-GHz-C(=CH2)-C
I2CH2-CCI(COC:I3)-0OGH3 and (CH3h C=CH-CI2-G(CH3)=GH-
A 55/45 mixture of Ll:H2-CCI(COCH3)-0OCH3 was obtained in 20% yield.

Potassium Jose μ-y diaate (11.04 g, 0.08 mole), hexachloroethane (4.96 g; 0.021 mole) and acetonitrile (20 c.c.) were mixed i under an argon atmosphere. 00' cc was added into a round bottom flask.

(C1h)2C=CH-C:I2-C(=CI2)-C
H2CH2-CH(COG)+3)-0OGlb and (CH3h C=CH-CTo-C(OH:+)
-〇〇-CH2-OH(COCH3)COOCHa 5
A 5/45 mixture (5.04 g; 0.02 mol) was added.

The reaction mixture was heated under reflux for 3 hours. After cooling, the reaction mixture was poured into water (100 cc) and then extracted with ethyl ether (3×50 cc). The organic phase was washed with water and then dried over magnesium sulfate. After filtration and evaporation of the solvent, (CH3) 2 C=CH-C1b-C(=CI2)-
CH2CI2-CGI (C:0CH3) -0OC1
b and (CH3) 2 C=CH-CH2-CCCHl) =
CH-CH2-C,CI (COCH3) -cooc
A 55/45 mixture of tii was obtained in the form of an orange oil with a yield of 95%.

Hexachloroethane (2.37 g; 0.01 mol), potassium carbonate (1.38 g; 0.01 mol), nitrous chloride (10 cc), and tionic acid (10 cc) were added to a 100 cc round bottom flask.

(GHa)2C<H-CIh-C(=CH2)
-CI2 CH7-CH (GOCH:+) -0OC
1b and (CH3hC=CI-CH2-C(CH3)=CH-C
)+2-CI(COCH3)-Cl]0CIL+ (1,26 g; 0.005 mol) was added.

The heterogeneous mixture was heated at 110° C. for 5 hours.

After extraction, (Oh)2G-CH-CH2-G(=CTo)-
CI2CH2-CCI CC0CH5)-0OCH3 and (CH3)2 C=CH-CH2-GCCH3)=CH
A 55/45 mixture of -C:I2-CTCl (COCH3)-0OClb was obtained in 78% yield.

Claims (1)

[Claims] 1. Formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (Ia) [In the formula, n represents an integer from 1 to 10, and X and Y are the same or different. -CHO, -COR_1, -COOR_2, -CONR_3R_4, -CN, -S
represents an electron-withdrawing group selected from O_2R_5 and -NO_2, where R_1, R_2, R_3, R_4 and R_5 each represent an alkyl group having 1 to 4 carbon atoms, and R_5 is unsubstituted or or a phenyl group substituted by methyl] with respect to two electron-withdrawing groups in the β-position, the method is capable of supplying a Cl^+ cation. Formula in which a halogenating agent is anionized with a base: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IIa) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IIb) [In the formula, n, X and Y is as defined above. 2. The halogenating agent is molecular chlorine, sulfuryl chloride, N-
The method according to claim 1, wherein the chlorosuccinimide or hexachloroethane is used. 3. The method according to claim 1 or 2, wherein the anionizing agent is an alkali or alkaline earth metal hydride, amide, hydroxide or carbonate, or a non-quaternized amine. 4. The method according to claim 1, 2 or 3, wherein the reaction is carried out at a temperature of 0 to 120°C. 5. The method according to claim 1 or 2, wherein the anionizing agent is an alkali metal alcoholate in the corresponding alcohol. 6. The method according to claim 5, wherein the reaction is carried out at a temperature lower than 0°C. 7. The method according to claim 5, wherein the reaction is carried out at a temperature lower than -30°C. 8. A process according to any of claims 1 to 7, in which an anionizing agent and a halogenating agent are added to the compound of formula (IIa) or (IIb) as a solution in an organic solvent. 9. A process according to any of claims 1 to 7, wherein the anionization of the compound of formula (IIa) or (IIb) is first carried out and then the halogenating agent is added. 10. When the reaction is carried out in an aliphatic hydrocarbon, aromatic hydrocarbon, ether, ketone, tertiary amide, nitrile, or nitrated solvent, or when the reaction is carried out in the presence of a phase transfer catalyst. 10. A method according to any one of claims 1 to 9, which is carried out in a chlorinated solvent.